Catalytic conversion of hydrocarbons



Patented Nov. 11, 1947- UNITED STATES PATENT orrlca CATALYTIC CONVERSION OF HYDROCARBONS Jacob It. Meadow, Memphis, Tenn., assignor to Socony-Vacuum Oil Company, Incorporated, a corporation of New York No Drawing. Application November 29, 1944,

' Serial No. 565,785

3Clailns. (01. 196-52) a solid adsorbent conversion catalyst containing a silica and an oxide of a metal which is difficult to reduce, for example, alumina, beryllia, zirconia, titania and the like. More specifically the invention is concerned, in certain preferred embodiments, with a process of that type in which a catalyst which has sufiered serious deterioration of activity is reactivated by a novel method of treatment hereinafter described.

Processes of catalytic conversion of the type to which this invention pertains are well known in the art. Outstanding examples are catalytic cracking and catalytic reforming, usually on silica-alumina, although composites of silica with a dificultly reducible metal oxide in general have been shown to be active. silica-alumina composites may be taken as typical for purposes of showing the objects and advantages of the invention.

In processes of catalytic cracking, a composite of the class defined above, e. g., a porous adsorb zs ent clay or synthetic composite of silica and alumina, is contacted with hydrocarbon vapors at conversion conditions, say, 800 to 1000 F. at atmospheric or greater pressure. The reaction which takes place is essentially a cracking to produce lighter hydrocarbons but is accompanied by a number of complex side reactions such as aromatization, polymerization, alkylation, etc. As a result of these complex reactions, a carbonaceous deposit is laid down on the catalyst which is commonly called coke, although it contains considerable hydrogen and is probably a highly condensed hydrocarbon. The coke tends to seriously impair the catalytic efficiency of the catalyst for the principal reaction and the conversion reaction is therefore, suspended aftercoke, to the extent of a few per cent by weight of catalyst, has accumulated on the catalyst. The catalytic surface is then regenerated by burning the coke in a stream of oxidizing gas and the catalyst is returned to the conversion stage of the cycle.

The catalyst also undergoes a second type of degeneration by reason of changes in the catalyst itself, as contrasted with the masking of catalytic surfaces by a coke deposit. As the catalyst is carried through a large number of cycles of alternate conversion and regeneration, the activity following each regeneration becomes progressively less until the activity is too low for economical use of the catalyst. These two types of degeneration differ in the time factor as well as in the nature of the change occurring. Coke deposition, which will be hereinafter called "contamination, is fairly rapid, it being desirable to remove the coke by burning after about 10 to 20 minutes on stream. This burning of the coke will be hereinafter designated as regeneration."

. On the other hand, the change in basic nature of the catalyst, resulting in lowered activity after regeneration, is a slow change. A catalyst may be in service for over a year of thirty minute cycles before becoming so degenerated as to require replacement. For example, a year or more may elapse before a catalyst in continuous service drops from an initial activity of 45, as hereinafter defined, to 25 or 30. This slow degeneration will be referred to herein as deactivation to distinguish it from contamination.

It is the primary object of this invention to Catalytic cracking 011 20 return a deactivated catalyst to a higher activity level by contacting a hydrocarbon vapor containing organic fluorides resulting from treatment of the hydrocarbon charge with hydrogen fluoride with the deactivated catalyst under conversion conditions of temperature and pressure. The process of treatment of catalysts with fluoride containing hydrocarbons in general is disclosed and claimed in copendin application Serial No. 565,786, filed November 29, 1944, by Frederick E. Ray, Russell Lee and the applicant herein. This treatment of the catalyst to raise the activity will be designated reactivation to avoid confusion with regeneration by burning of a combustible deposit.

The nature of the deactivation is not understood and it is, therefore, impossible to aiiord a clear explanation of reactivation as practiced according to thisinvention. It has been noted that X-ray diffraction patterns show crystalline matter in catalyst deactivated by aging and it may be that high catalytic activity is associated with the amorphous state. On that assumption, it may be postulated that reactivation with alkyl fluoride causes reversion of crystalline matter to an amorphous form which is more active. However, it may also be suggested that the reactivation is due, not to a return of the catalyst to its original form, but to formation of active compounds such as aluminum fluoride, silicon tetrafluoride which reacts with aluminum oxide to form a non-volatile complex, or the like. If that be the true explanation, the reactivation is, in efiect, the conversion of deactivated catalyst to a new composition of matter'difiering in chemical 3 nature from but similar in activity to the original catalyst.

The invention is, of course, not limited to any theory of operation, but it is believed that the effects obtained are due to the presence in the conversion zone of nascent hydrogen fluoride form by catalytic decomposition of the organic fluorides. Efiects of somewhat the same general nature may be obtained by the use oi hydrogen fluoride gas, but this appears to be undesirable in that hydrogen fluoride so introduced is less effective when used in amounts and under conditions to avoid substantial decomposition of the catalyst. It appears that small amounts of nascent hydrogen fluoride, if that be the active principal, are vastly superior to hydrogen fluoride introduced as such.

The amount of organic fluoride introduced according to the present invention should be kept relatively low. In general, less than 1% by weight based on total vapor charge of fluorine in the form of organic fluoride is preferred. Larger amounts up to about 3% may be used, but without marked advantage. When still larger amounts of fluorides are present, the treatment tends to cause serious damage to the catalyst. The preferred procedure is to conduct the fluoride containing vapor over the catalyst in the same manner and under the same conditions as those employed for conducting the principal reaction. Preferably, the treatment is made in a plurality of cycles with a hydrocarbon fraction containing standard, although both catalysts may have the tion with catalysts sensitive to overtreatment,

suitable care should be exercised. It is noted that most catalysts do not show such sensitivity under conditions employed so far.

The benefits of the invention are illustrated by a series of cycles in which a catalyst was alternately on stream for conversion of gas oil at 800 F. and atmospheric pressure and in regeneration for burning of coke. During the conversion side of the cycle, oil was supplied at a space velocity of 1.5 volumes of liquid oil per volume of catalyst per hour and one volume of liquid oil was contacted with four volumes of catalyst during each cycle. The catalyst was a synthetic silica-alumina coprecipitate. During certain of the cycles, the charge stock supplied (treated gas oil) was gas oil which had been treated with hydrogen fluoride in liquid phase to separate sulfur and asphaltic compounds while propylene was added during such treatment with hydrogen fluoride to alkylate compounds in the charge susceptible to alkylation.

The yields obtained on treated gas oil are not necessarily comparable with each other or with yields on standard gas oi because of differa very small amount of fluorides; for example;

up to about 0.3% fluorine by weight. It is to be understood that use of the term "cycle in the specification is not intended to refer only to fixed bed operation wherein hydrocarbons and regeneration air are alternately passed through a stationary mass of catalyst. Continuous operations ences in nature and history of the charge. The significant values are the yields on standard gas oil which is the gas oil cut of Oklahoma City crude. The yield of gasoline from the standard charge is regarded as the index of activity of the catalyst.

Table 1- below shows the results obtained.

TABLE I Actiziation of fresh catalyst Cracking Yields Fluorine Cumula Charge Stock, Content, No. of five No 410 F.

Description Per Cent Cycles of C g Gas, Coke, E. P. Gasoline Gasoline wt. y Per Cent Per Cent Gasoline, to Coke to Gas wt. wt. Per Cent Ratio Ratio vol.

Stmidard Gas Oil. Nil 8 8 6.5 2. 9 43.0 14.811 6.621 Treated Gas Oil 0.19 5 13 11.5 4.5 38.4 8.5:1 3.3:1 Do 0.01 7 20 6.2 1.4 44.4 10.1:1 7.2:1 5 25 11.5 3.7 40.0 10.8:1 3.5:1 Nil 5 30 5.9 3.0 46.6 15. 5:1 7. 9:1 0. 11 5 35 i2. 9 3. 9 4.1.9 10. 7:1 3. 3:1 0.28 4 39 16.6 5.0 40.6 8.111 2.421 0.06 5 44 8.7 4.5 45.4 10.1:1 5.2:1 0.01 5 49 7.3 4.7 47.3 10.1:1 6.5:1 Nil 5 54 6.5 3.4 49.7 14.6:1 7.7:1

in which the catalyst passes alternately through a reaction zone for contact with charge and a regeneration zone are well adapted to the purposes of the invention. In the latter case, a cycle indicates the average interval required for catalyst to complete the circuit through reactor and regenerator. Fixed bed runs reflect the advantages of the invention more accurately since each catalyst particle is contacted in the same manner during successive cycles, and the results reported herein are of that type.

The ratio between the time a catalyst may be employed for cracking and the time spent in regeneration is a function of the rate of coke formation. Thus a catalyst which forms twice as much coke is actually only half as eflicient as the The above table shows significant increases in activity when a relatively active catalyst is used. The invention may thus be used to activate fresh catalyst. However, the treatment is somewhat drastic when compared to the increase in activity of the catalyst. Catalysts activated according to the present invention show a faster rate of decrease in activity during use than catalysts not so activated, and it is believed that the principal value of the invention is restoration of the activity of the catalyst which has become deactivated over a long period of use. Such deactivated catalyst was used in a series of cycles similar to those of Table I. The catalyst was similar to that of Table I except that it had been in service in a commercial unit for a period of 5 time sumcient to decrease its activity to 28.3. The results of this second series are reported in Table II below.

one cycle with vapor of a hydrocarbon fraction which has been previously treated with hydrogen fluoride and which vapor containsorganic fluo- TABLE 11 Activation of used catalyst Cracking Yields Fluorine Charge Stock, Content, No. of g g g' 410 F.

Description Per Cent Cycles of e165 Gas, Coke, E. P. Gasoline Gasoline wt. y Per Cent Per 0 nt Gasoline, to (Joke to Gas wt wt. Per Cent Ratio Ratio vol.

Standard Gas Oil Nil 8 3 4.4 1.8 28.3 15. 7:1 6. 4:1 Treated Gas Oil 0.28 5 8 12.3 3.2 33.9 10.6:1 2.8:! Standard Gas Oil Nil 5 13 5.4 2.0 37.0 18. 5:1 6. 8:1 Treated Gas Oil" 0.28 4 17 14.5 3.4 38.3 11.3:1 2.6:1 Standard Gas OiL Nil 3 20 6.2 2.0 40.3 20.1:1 7.7:1 Treated Gas Oil 0.28 6 26 13.5 3.3 38.9 11.821 2.911 Standard Gas Oil Nil 7 33 5.1 4. 2 40. 9 9.821 8.021

Table II illustrates the possibility of overtreating. After the first series with fluoride containing oil, the activity, gasoline to coke ratio and gasoline to gas ratio were all improved to a marked extent. The second series of treatment with fluorides yielded some improvement, but the third series resulted in an overall deterioration of the catalyst. While the activity was slightly increased, the more than 50% reduction in the gasoline to coke ratio is regarded as serious loss in economic value of the catalyst.

To illustrate that the efiect obtained is attributable to organic fluorides in the charge stock, a series was run using a gas oil in which. a small amount of propyl fluoride had been dissolved. The results appear in Table III below.

rides in an amount not substantially greater than mina for a predetermined period of time to convert said hydrocarbons with concurrent deposition of a combustible deposit on the catalyst which substantially lowers the catalytic efliciency thereof, followed by burning regeneration of the catalyst and return of the catalyst to conversion of hydrocarbons thus completing a cycle of opera- TABLE III Activati n of fresh catalyst Cracking Yields Fluorine Charge Stock, Content, No. of 410 F.

Description Per Cent Cycles of 0 816's Gas, Coke. E. P. Gasoline Gasoline wt. y Per Cent Per Cent Gasoline, to Coke to Gas wt. wt. Per Cent Ratio Ratio vol.

Standard G8 011. Nil 5 5 6.5 '29 43.0 14.8:1 6. 6:1 Treated G88 Oil" 0.29 5 10 14.8 4. 5 47.4 10.5:1 3.2:1 Standard G88 Oil- Nil 4 14 7. 7 3. 2 48. O 15. 021 6. 2:1

.I claim: 1. In a process for conversion of hydrocarbons wherein hydrocarbon vapors are contacted with a solid porous catalyst containing silica and alumina for a predetermined period of time to convert said hydrocarbons with concurrent deposition of a combustible deposit on the catalyst which substantially lowers the catalytic efficiency thereof, followed by burning regeneration of the catalyst and return of the catalyst to conversion 01 hydrocarbons thus completing a' cycle of operation which is repeated until the catalyst is deactivated to a substantial extent by effects other than said combustible deposit as evidenced by the fact that burning regeneration of the catalyst after a series of cycles regenerates the catalyst to an activity as measured by per cent conversion of said hydrocarbons lower than the activity of the catalyst at the beginning of said series; the improvement which comprises treating said catalyst at a time when the catalyst is deactivated to an activity following burning regeneration lower than contacting said catalyst at such time in at least after a series of cycles regenerates the catalyst to an activity as measured by per cent conversion of said hydrocarbons lower than the activity of the catalyst at the beginning of said series; the-improvement which comprises treating said catalyst at a time'when the catalyst is deactivated to an activity following burning regeneration lower than the activity at the beginning of said series by cona tacting said catalyst at such time in at least one cycle with vapor of hydrocarbon fraction which has been previously treated with hydrogen fluoride Y and which vapor contains organic fluorides in an amount not substantially greater than 1% by weight as a. result of such treatment, and after contacting said catalyst with said fluoride containing vapor, again contacting hydrocarbon vapor substantially free of fluorides with said catalyst.

3. In a process for conversion of hydrocarbons wherein hydrocarbon vapors are contacted with 7 a solid porous catalyst containing silica and alumina for a predetermined period of time to convert said hydrocarbons with concurrent deposition of a. combustible deposit on the catalyst which substantially lowers the catalytic efllciency thereof, followed by burning regeneration of the catalyst and return of the catalyst to conversion of hydrocarbons thus completing a cycle of operation which is repeated until the catalyst is deactivated to a substantial extent by effects other than said combustible deposit as evidenced by the fact that burning regeneration of the catalyst after a series of cycles regenerates the catalyst to an activity as measured by per cent conversion of said hydrocarbons lower than the activity of the catalyst at the beginning of said series; the improvement which comprises treating said catalyst at a time when the catalyst is deactivated to an activity following burning regeneration lower than the activity at the beginning of said series by contacting said catalyst at such time in a plurality of cycles with vapor of a hydrocarbon fraction which has been previously treated with hydrogen fluoride and which vapor contains organic fluorides in an amount not substantially greater 8 than 0.3% by weight as a result of such treatment, and after contacting said catalyst with said fluoride containing vapor, again contacting hydrocarbon vapor substantially free of fluorideswith said catalyst.

JACOB R. MEADOW.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS OTHER REFERENCES Journal of Organic Chemistry, vol. 3, 1938, pages 26-32. 

